JP6984012B2 - Compositions, methods and test kits for determining authenticity - Google Patents

Description

The present application describes compositions containing at least one leuco composition and the use of these compositions in identifying genuine ones from counterfeit products. The leuco composition is provided in a stable, colorless or substantially colorless state and incorporated into the target composition. The present application further relates to a method for determining an authentic composition comprising at least one leuco composition. The present application further relates to a test kit for detecting an authentic composition containing at least one leuco composition.
Background of the Invention The manufacture and sale of counterfeit products is an ever-increasing problem in the consumer packaging industry. Counterfeit products are generally of lower quality compared to the branded products they imitate. Counterfeit products can be harmful to a brand by diverting profits and associating low quality and ineffective products with the brand name. Counterfeit products can also be dangerous to consumers. The use of poor quality and ineffective raw materials can be harmful to consumer health.

Packaging solutions have been developed to reduce the risk of counterfeit products being sold as genuine. Such solutions include open seals, incorporation of holograms and color shift inks into label graphics, and unique packaging designs. However, these solutions can be counterfeited in their own right and are ineffective if the counterfeit product is filled in the original container. Therefore, there is still a continuing need for a quick and easy way to detect the authenticity of a product that does not affect the quality or functionality of the product.

Therefore, it would be beneficial to provide compositions, quick and easy methods, and test kits for detecting the authenticity of a product without affecting the quality or functionality of the product.
Description of the Invention The present disclosure relates to a composition comprising at least one leuco composition, wherein the composition is the first color at any time through manufacture, transportation, storage and storage and normal product use. The leuco composition can change from a colorless or substantially colorless state to a colored state in the presence of sufficient inducer, thereby changing the laundry care composition from a first color to a second color. Change.

The present disclosure provides a composition comprising at least one laundry care ingredient and at least one leuco composition. The composition is a material that is easily counterfeited, such as a perfume composition, a fuel composition, a lubricating oil composition, a thermoplastic polymer composition, a polyol composition, a polyurethane composition or a seed coating composition. In a preferred embodiment, the leuco composition is of formula (I) :.
Ar ¹ Ar ² Ar ³ CH (I)
[In the formula, Ar ² and Ar ³ are independently carbocyclic aryls or heteroaryls, and Ar ¹ is selected from the group consisting of unsubstituted phenyl, electron-deficient carbocyclic aryls and heteroaryls. ] Containing at least one leuco compound conforming to.

The present disclosure is a method of detecting an authentic composition, a) a step of preparing a composition having a first color and containing at least one leuco composition; and b) an inducer in the composition. And the step in which the inducer is sufficient to achieve a change from a colorless state to a colored state in at least one leuco composition; c) the first color in the composition. Also provided is a process of detecting a change from a first color to a second color, comprising a step in which the change from the first color to the second color is visually perceptible.

The present disclosure is a test kit for determining the authenticity of a composition, a) a container for receiving a certain amount of the composition; b) an inducer to convert the leuco composition; c) the composition. And a test kit containing instructions for detecting the authentic composition in combination with the inducer is also provided.
If DETAILED DESCRIPTION defined used herein the invention, the term "alkoxy", C ₁ -C ₈ alkoxy and alkoxy derivatives of polyols having a repeating unit, for example butylene oxide, glycidol oxide, to include ethylene oxide or propylene oxide Intended.

As used herein, the interchangeable terms "alkyleneoxy" and "oxyalkylene" and the interchangeable terms "polyalkyleneoxy" and "polyoxyalkylene" are generally the following repeating units: -C ₂ H ₄ Refers to a molecular structure containing one or more of O-, -C ₃ H ₆ O-, -C ₄ H _{8 O-, and any combination thereof.} Non-limiting structure corresponding to these groups, for _{example, -CH 2 CH 2 O -,} - CH 2 CH 2 CH 2 O -, - CH 2 CH 2 CH 2 CH 2 O -, - CH 2 CH ( Includes CH ₃ ) O- and -CH ₂ CH (CH ₂ CH ₃ ) O-. Further, the polyoxyalkylene component may be selected from the group consisting of one or more monomers selected from _{C 2-20 alkyleneoxy groups, glycidyl groups, or mixtures thereof.}

The terms "ethylene oxide", "propylene oxide" and "butylene oxide" may be referred to herein by their typical designations "EO", "PO" and "BO" respectively.

As used herein, the terms "alkyl" and "alkyl capped" mean any monovalent group formed by removing a hydrogen atom from a substituted or unsubstituted hydrocarbon. Intended to do. Non-limiting examples include the C ₁ -C ₁₈ alkyl groups and one side surface including a C ₁ -C ₆ alkyl group, including branched or unbranched, and substituted or unsubstituted hydrocarbyl moiety.

As used herein, unless otherwise specified, the term "aryl" is intended to include _{C 3 to} C _{12 aryl groups.} The term "aryl" refers to both carbocyclic and heterocyclic aryl groups.

As used herein, the term "alkali" refers to any alkyl-substituted aryl substituents and aryl-substituted alkyl substituents. More specifically, the term intended to refer to the additional substituents may not include also comprise, C _{7 to 16} alkyl-substituted aryl substituents and C _{7 to 16} aryl-substituted alkyl substituents Has been done.

As used herein, the term "detergent composition" is a subset of a laundry care composition and includes cleaning compositions including, but not limited to, products for washing fabrics. Such compositions may be pre-treated compositions for use prior to the cleaning step, rinse-added compositions, and cleaning aids such as bleaching additives and "stain sticks" or pre-treated types. May be.

As used herein, the term "laundry care composition" refers to products for washing fabrics, textile softening compositions, textile-enhancing compositions, textile cleansing compositions and textile care and, unless otherwise indicated. Granules, powders, liquids, gels, pastes, single-dose packages, bar-form and / or flake-type detergents and / or textile treatment compositions, and those, including but not limited to other products for maintenance. Including the combination of. Such compositions may be pretreated compositions for use prior to the cleaning step, rinsed compositions, and cleaning aids such as bleaching additives and / or "stain sticks" or pre. A product containing a treatment composition or a substrate, for example, a dryer-added sheet may be used.

As used herein, the term "leuco" (eg, when used with respect to a compound, moiety, radical, dye, monomer, fragment or polymer) is used upon exposure to a specific chemical or physical incentive. An entity (eg, an entity) subject to one or more chemical and / or physical changes that results in a shift from a first color state (eg, uncolored or substantially colorless) to a second, more highly colored state. Refers to an organic compound or a part thereof). Suitable chemical or physical incentives include, but are not limited to, oxidation, pH changes, temperature changes, and changes in electromagnetic radiation (eg, light) exposure. Suitable chemical or physical changes appearing in leuco entities include, but are not limited to, oxidative and non-oxidative changes such as intramolecular cyclization. Therefore, in one aspect, a suitable leuco entity can be a reversibly reduced form of the chromophore. In one aspect, the leuco moiety preferably incorporates a first and second π system upon exposure to one or more of the chemical and / or physical incentives described above, a third combined conjugate π. It includes at least the first and second π systems that can be converted into systems.

As used herein, the term "leuco composition" or "leuco colorant composition" is used as at least two leuco compounds having independently selected structures, as described in more detail herein. Refers to a composition comprising.

As used herein, the "average molecular weight" of leuco colorants is reported as weight average molecular weight, as determined by their molecular weight distribution, and as a result of their manufacturing process, the leuco colorants disclosed herein. May contain a distribution of repeating units in their polymer moieties.

As used herein, the terms "maximum extinction coefficient" and "maximum molar extinction coefficient" are used at wavelengths of maximum absorption (also referred to herein as maximum wavelength) in the range of 400 nanometers to 750 nanometers. It is intended to describe the molar extinction coefficient.

As used herein, the term "first color" is used to refer to the color of a pre-triggered laundry care composition and is intended to include any color, including colorless and substantially colorless. There is.

As used herein, the term "second color" is used to refer to the color of a post-induction laundry care composition, via visual inspection, or the use of analytical techniques such as spectrophotometric analysis. In any, it is intended to include any color identifiable from the first color of the laundry care composition.

As used herein, the term "converter" refers to any oxidizing agent known in the art other than molecular oxygen in any of its known forms (singlet and triplet states).

As used herein, the term "inducing agent" refers to a reactant suitable for converting a leuco composition from a colorless or substantially colorless state to a colored state.

As used herein, the term "whitening agent" in white cotton, on a cloth, has a relative hue angle of 210-345, or even 240-320, or even 250-300 (eg, 250-300). Refers to a dye or a leuco colorant that can form a dye when induced, as long as it provides a hue with a relative hue angle of 250-290).

As used herein, a "cellulosic substrate" is intended to include any substrate that contains at least a majority of cellulose by weight. Cellulose can be found in wood, cotton, linen, jute and hemp. The cellulosic substrate may be in the form of powders, fibers, pulp and articles formed from powders, fibers and pulp. Cellulose-based fibers include, but are not limited to, cotton, rayon (regenerated cellulose), acetate (cellulose acetate), triacetate (cellulose triacetate), and mixtures thereof. Articles formed from cellulosic fibers include textile articles, such as woven fabrics. Articles made from pulp include paper.

As used herein, articles such as "a" and "an" are understood to mean one or more of those claimed or described, as used in the claims.

As used herein, the terms "include / s" and "including" mean non-limiting.

As used herein, the term "solid" includes granules, powders, bars and tablet product forms.

As used herein, the term "fluid" includes liquid, gel, paste and gas product forms.

The test methods disclosed in the Test Methods section of this application should be used to determine the respective values of the parameters of the applicants' invention.

Unless otherwise noted, all ingredient or composition levels refer to the active part of that ingredient or composition and impurities, eg, which may be present in a commercial source of such ingredient or composition. Exclude residual solvents or by-products.

All percentages and ratios are calculated by weight unless otherwise specified. All percentages and ratios are calculated based on the total composition unless otherwise indicated.

As used herein, the term "electron-deficient carbocyclic aryl group" refers to a C ₃ -C ₁₂ carbocyclic aryl group having an electron withdrawing group covalently bonded to an aryl group.

As used herein, unless otherwise specified, the term "heteroaryl" means that at least one ring carbon is -O-, -S-, -N =, -N (R)-, and them. It is replaced by a heteroatom selected from mixtures and, where, R represents not hydrogen, refers to a C ₃ -C ₁₂ aryl group.

The term "substituted heteroaryl" is in which at least one ring carbon is replaced with a heteroatom selected from -O-, -S-, -N =, -N (R)-, and mixtures thereof. , an atom or group other than hydrogen, covalently bound to any ring atom of a heteroaryl refers to a C ₃ -C ₁₂ aryl group.

As used herein, the term "electron donating substituent" donates a portion of its electron density to a conjugated π system via resonance or inducing effects, thereby making the π system more nucleophilic. Refers to an atom or functional group. When attached to a benzene molecule, the electron-donating substituent is more likely to be involved in the electrophilic substitution reaction. Benzene itself will normally undergo substitutions with electrophiles, but additional substituents can cause reaction rates or products by electronically or sterically affecting the interaction of the two reactants. Can be modified. Electron-donating substituents are often known as activating groups. Suitable electron donating radicals are tertiary amines (-NR ₂ ), secondary amines (-NHR), primary amines (-NH ₂ ), ethers (-OR), thioether (-SR) hydroxy. (-OH), thiol (-SH), amide (-NHC (O) R), ester (-OC (O) R), alkyl (-R), phenyl (-C ₆ H ₅ ) and vinyl, eg Including, but not limited to (-CH = CH ₂ , -CH = CHR, -CR = CH ₂ , -CR = CHR), where R represents an organic radical.

As used herein, the term "electron-withdrawing substituent" refers to an atom or functional group that removes the electron density from the π system to make the π system more electrophilic. When attached to a benzene molecule, electron-withdrawing substituents make the electrophilic aromatic substitution reaction slower and more complex. Electro-attractive substituents are often referred to as inactivating groups. Suitable electron-withdrawing substituents are trihalide (eg, -CF _{3 , -CCl 3} ), cyano (-CN), sulfonate (-SO ₃ H), sulfonic acid ester (-SO ₃ R), sulfone (-SO). ₂ R), sulfoxide (-S (O) R), ammonium _(-NH 3 +), quaternary amine _(-NR 3 +), nitro _(-NO 2), aldehyde (-C (O) H), Ketone (-C (O) R), carboxylic acid (-COOH), carboxylic acid ester (-C (O) OR), acyl chloride (-C (O) Cl), amide (-C (O) NH ₂ , Includes, but is not limited to, -C (O) NHR, -C (O) NR ₂ ) and halides (eg, F). Carbocyclic aryl groups have multiple substituents in which a carbocyclic aryl group is present and the substituents are a mixture of electron-withdrawing and electron-donating substituents, or if the structure of the substituents is unknown. The determination of whether or not is electron-deficient may be made by following the method "determination of electron-deficient carbocyclic aryl ring" as presented herein. The method is only applicable if there is a mixture of electron-withdrawing and electron-donating substituents.
Composition The present disclosure relates to a composition comprising a leuco composition. Leuco dyes are known to exhibit a change from a colorless or slightly colored state to a colored state upon exposure to specific chemical or physical incentives. The changes in color that appear are typically visually perceptible to the human eye. The color change upon induction is a change in the molar attenuation coefficient of the leuco dye molecule (also known in some literature as the molar extinction coefficient, the molar absorption coefficient and / or the molar absorption rate) in the range of 400 to 750 nm. It arises from.

Leuco dyes are also known, for example, as bluish or hue-imparting agents that can mask the yellowing of textiles. These leuco dyes can change from a first color to a second color during the washing process. These leuco dyes can also be deposited on textiles, which allows for a whitening effect.

Traditional leuco dyes can serve the purposes mentioned above, but can change from a first color state to a second color state over time, thereby the appearance of the product to which they are added. And because it alters functionality, it is unsuitable for use as an anti-counterfeit agent.

Surprisingly, it has now been found that compositions containing the currently claimed Leuco composition undergo a color change only when in contact with sufficient inducers. As such, leuco compositions do not affect the quality or functionality of the composition through manufacturing, transportation, storage or storage; but only if tested for authenticity. In addition, leuco compositions may not deposit on the fabric, thereby preserving the validity of the composition for use in all fabric types and colors.

The present disclosure relates to a composition comprising at least one leuco composition. In a preferred aspect, the leuco composition is of formula (I) :.
Ar ¹ Ar ² Ar ³ CH (I)
In the formula, Ar ² and Ar ³ are independently carbocyclic aryls or heteroaryls, and Ar ¹ is an unsubstituted phenyl, electron-deficient carbocyclic compound. It is selected from the group consisting of aryl and heteroaryl. Ar ¹ is preferably selected from the group consisting of unsubstituted phenyl, nitro-substituted carbocyclic aryl, furan, thiophene, pyridine and indole. More preferably, Ar ¹ is furan. The expression of the above formula (I) does not imply or limit the arrangement of the substituent Ar group.

The composition may contain at least one leuco composition conforming to the formula (I) as described above, in which at least one of Ar ² and Ar ³ is an electron donating group. It is a substituted phenyl ring. The electron donating group is preferably a substituted amine covalently bonded to the phenyl ring at the para position with respect to the carbon atom connecting the three Ar groups. More preferably, the substituted amine is of the formula −NR ⁴ R ⁵ [in the formula, R ⁴ and R ⁵ are H, C _1-16 branched alkyl, C _1-16 linear alkyl, C _{1-16, respectively.} Selected independently from substituted branched alkyl, C _1-16 substituted linear alkyl, C _7-16 substituted alkaline, C _7-16 unsubstituted alkaline, polyoxyalkylene, and mixtures thereof] ..

Even more preferably, the composition may contain at least one leuco composition conforming to formula (I) as described above, in which ^{both Ar 2} and Ar ³ contain three Ar groups. It is a phenyl ring having an independently selected substituted amine that is covalently bonded to each phenyl ring at the para position with respect to the carbon atom connecting the above. Substituted amines may ^{be compatible with Formula-NR 4} R ^{5 , where R 4} and R ⁵ , respectively, are H, C _1-16 branched alkyl, C _1-16 linear alkyl, C. _{It is independently selected from 1-16} substituted branched alkyl, C _1-16 substituted linear alkyl, C _7-16 substituted alkaline, C _7-16 unsubstituted alkali, polyoxyalkylene, and mixtures thereof.

The composition described above may contain at least one leuco composition conforming to formula (I) as described above and may resist deposition on textiles. The leuco composition may resist deposition on textiles, for example by increasing its solubility in wash water. If the affinity of the leuco composition for wash water is greater than its affinity for textiles, the leuco composition will have low realism for textiles. Therefore, the leuco composition may contain a solubility enhancing substituent. Such polar solubilizing groups may include both nonionic and ionic polar solubilizing groups.

Solubility-enhancing substituents may contain substituted amines suitable ^{for formula-NR 4} R ⁵ as described above, wherein at least one of ^{R 4} and R ^{5 is polyoxyalkylene in the formula.} Of R ⁴ and R ⁵ , at least two, at least three, and four may be polyoxyalkylenes. The polyoxyalkylene may be a polyoxyethylene polymer having 2 to 300 ethylene oxide repeating units. The polyoxyalkylene is preferably a polyoxyethylene polymer having 2 to 100 ethylene oxide repeating units. More particularly preferred are polyoxyethylene polymers having 2 to 50 ethylene oxide repeating units. It is preferred that at least one polyoxyalkylene polymer has at least three oxyalkylenes, preferably ethylene oxide, repeating units.

Polyoxyalkylene is a formula (II):
-(EO) _b (PO) _c (II)
May be represented by, where the polyoxyalkylene comprises b ethylene oxide units and c propylene oxide units in any sequence, one such unit being the nitrogen of the polyoxyalkylene substituted amine. Covalently bonded to an atom. Preferably, the ethylene oxide (“EO”) unit is covalently attached to the nitrogen atom of the polyoxyalkylene substituted amine. Subscript b is in the range of 2 to 300, preferably 2 to 100, more preferably 2 to 15; subscript c is the propyleneoxy (“PO”) unit in the polyoxyalkylene. B) represents the number, and is in the range of 0 to 60, preferably 0 to 20, and more preferably 0 to 10.

The viability of the leuco composition on the textile may be measured by the mol% of the leuco composition deposited on the textile during a typical washing cycle. During a typical wash cycle, less than 10 mol%, preferably less than 5 mol%, more preferably less than 1 mol%, even more preferably less than 0.5 mol% of the laundry care composition is a textile. Accumulate in.

It may be acceptable for the leuco composition to substantially deposit on the textile during a typical wash cycle. The resistance of the leuco composition to the conversion from a colorless or substantially colorless state to a colored state in the absence of sufficient inducer may make the deposition on the textile invisible to the user. Therefore, the reality of leuco compositions for textiles may be greater than 10 mol%, greater than 15 mol%, and even greater than 25 mol%.

The leuco composition of the present disclosure is of formula (III) :.

In the formula, ^{both Ar 2} and Ar ³ are covalently bonded to their respective phenyl rings at the para position with respect to the carbon atom connecting the three Ar groups. It is a phenyl ring with an independently selected substituted amine-NR ⁴ R ^5. Ar ¹ is preferably an electron-deficient carbocyclic aryl, where the subscript a is an integer of 1-5.

The leuco compositions of the present disclosure are more preferably of formula (IV) :.

In the formula, Ar ¹ is furan, and ^{both Ar 2} and Ar ³ are covalently bonded to their respective phenyl rings at the para position with respect to the carbon atom connecting the three Ar groups. to which, with a substituted amine -NR ⁴ R ⁵ which is selected independently, is a phenyl ring.

Even more preferably, the leuco composition of the present disclosure is of formula (IV) :.

In the equation, each n is independently an integer of 2 to about 300, more preferably 2 to about 100, even more preferably 2 to 50, and most preferably each n. Are independently integers of 2 to about 25; each X is independently selected from the group consisting of H, alkyl, alkylcarboxylates and aryl carboxylates. More preferably, each X is H.

The amount of leuco colorant used in the composition of the present invention may be at any level suitable for achieving the object of the present invention. In one aspect, the composition is about 0.0001% by weight to about 1.0% by weight, preferably 0.0005% by weight to about 0.5% by weight, even more preferably about 0.0008% by weight to about 0%. It contains 2% by weight, most preferably 0.004% by weight to about 0.1% by weight, leuco colorant.

In another aspect, the composition is 0.0025 to 5.0 mm equivalent / kg, preferably 0.005 to 2.5 mm equivalent / kg, even more preferably 0.01 to 1.0 mm equivalent / kg. Most preferably, it comprises an amount of 0.05 to 0.50 m / kg of leuco colorant, where the unit of milliequivalent / kg refers to the milliequivalent of the leuco portion per kg of composition. For leuco colorants containing more than one leuco moiety, the milliequivalent number is related to the milliequivalent number of leuco colorants according to the following equation: (mole of leuco colorant) x (milli equivalent of leuco moiety / leuco). Number of millimole of colorant) = milliequivalent of leuco portion. In the case where there is only a single leuco moiety per leuco colorant, the milliequivalent number / kg is equal to the millimolar number / kg of the leuco colorant in the composition.

The molar extinction coefficient of the colored state at the maximum absorbance at a wavelength in the range of 200 to 1,000 nm (more preferably 400 to 750 nm) is preferably at least 5 of the colorless state at the wavelength of the maximum absorbance of the colored state. The molar extinction coefficient is fold, more preferably 10 fold, even more preferably 25 fold, most preferably at least 50 fold. Preferably, the molar extinction coefficient of the colored state at maximum absorbance at wavelengths in the range of 200-1,000 nm (more preferably 400-750 nm) is at least 5 times that of the colorless state within the corresponding wavelength range. The maximum molar extinction coefficient is preferably 10-fold, even more preferably 25-fold, most preferably at least 50-fold. Those of skill in the art will find that these ratios may be much higher. ^{For example, the colorless state may have a maximum molar extinction coefficient of only 10M -1} cm ^-1 at wavelengths in the range of 400-750 nm, and the colored state may have a maximum molar extinction coefficient in the range of 400-750 nm. , 80,000 M ^-1 cm ^-1 or higher may have a maximum molar extinction coefficient, in which case the ratio of extinction coefficients will be 8,000: 1 or higher.

The maximum molar extinction coefficient of the colorless state at wavelengths in the range of 400 to 750 nm is ^{less than 1000 M -1} cm ^-1 , and the maximum molar extinction coefficient of the colored state at wavelengths in the range of 400 to 750 nm is 5. , ^{000M -1 cm} -1 greater, preferably 10,000,25,000,50,000 or even 100,000 m ^-1 cm ^-1 greater. Those skilled in the art may have a polymer containing more than one leuco moiety having a significantly higher maximum molar extinction coefficient in the colorless state (eg, convert to the additive effect or colored state of the leuco moiety diversity). You will recognize and understand (due to the presence of one or more Leuko moieties).

The colored state of the leuco composition may have a maximum absorbance (λ _max ) at a wavelength of 400 to 700 nm. Preferably, the colored state λ _max of the leuco composition may be outside the range of 520 to 620 nm. More preferably, the colored state λ _max of the leuco composition may be 625 to 655 nm.

The composition of the present invention can be any composition or product that is easily counterfeited. Suitable examples of such compositions or products include, but are not limited to, branded consumer products and branded intermediate goods. In a preferred embodiment, the present invention provides a fragrance composition, a fuel composition, a lubricating oil composition, a thermoplastic polymer composition, a polyol composition, a polyurethane composition, or a seed coating composition.

The perfume composition according to the present invention can contain any suitable perfume raw material. A typical fragrance or fragrance consists of a fragrance "top note" and a fragrance bottom note. The top note of the fragrance is the fragrance material that is immediately perceived at the time of application of the fragrance, while the bottom note is the material that is perceived long after the application. In addition to perfume top and bottom notes, perfume adjuvants are also used to impart additional benefits such as color, specific light resistance, chemical stability, and the like. Although detailed descriptions of the properties and types of adjuvants commonly used in perfume bases cannot be comprehensive, the ingredients are well known to those of skill in the art. However, specific non-limiting examples may include: viscous agents (eg, surfactants, thickeners, gelling and / or rheology modifiers), stabilizers (eg, eg). Preservatives, Antioxidants Heat / Light and / or Buffers or Chelating Agents, such as BHT), Colorants (E.g. Dyes and / or Pigments), Preservatives (E.g. Antibacterial or Antibacterial or Antifungal or Antistimulants) ), Abrasives, skin coolers, fixatives, insect repellents, ointments, vitamins and mixtures thereof. Other suitable fragrance adjuvants that may be optionally used are tertiary amines and alcohols, especially those with high water solubility, such as triethanolamine, methyldiethylamine, methyldiethanolamine, ethanol, propanol and the like. Can be done. In addition to the above raw materials, the above-mentioned leuco composition and leuco compound are added to the fragrance composition in an amount of 0.001 to 1% by weight, preferably 0.001 to 0.5%, most preferably 0.001 to 0. It can be added in an amount of 1%.

The fuel composition according to the present invention may contain any suitable fuel material. Suitable fuel compositions include, but are not limited to, gasoline, diesel, kerosene, biodiesel, or other alcohol-based fuels. The leuco composition can be added to the fuel composition in an amount of 0.001 to 1% by weight, preferably 0.001 to 0.5%, most preferably 0.001 to 0.1%. The fuel composition may further include other additives such as anti-knock agents, methylcyclopentadienyl manganese tricarbonyls, antioxidants, metal deactivating agents, detergents and alcohols.

The lubricating oil composition according to the present invention may contain any suitable lubricating oil raw material. Suitable lubricating oil compositions include, but are not limited to, engine oils, automatic transmission fluids, gear oils, hydraulic fluids, turbine oils, transformer oils and compressor oils. The above-mentioned leuco composition and leuco compound are added to the lubricating oil composition in an amount of 0.001 to 1% by weight, preferably 0.001 to 0.5%, and most preferably 0.001 to 0.1%. can do. Lubricating oil compositions may further include other additives such as dispersants, antioxidants, anti-wear agents, detergents, corrosion inhibitors, metal deactivators, viscosity modifiers and friction modifiers.

The thermoplastic polymer composition according to the present invention can contain any suitable thermoplastic polymer and thermoplastic polymer additive. Suitable thermoplastic polymers are polyester, polyamide, polyolefin, acrylic, acrylonitrile butadiene styrene, polylactic acid, polybenzimidazole, polycarbonate, polyether sulfone, polyoxymethylene, polyether ether ketone, polyetherimide, polyphenylene oxide, polyphenylene sulfide. , Includes, but is not limited to, polyvinyl chloride, polytetrafluoroethylene and polystyrene. Suitable polyolefins include, but are not limited to, polyethylene, polypropylene, polymethylpentene and polybuta-1-ene. Thermoplastic compositions include other additives such as antioxidants, nucleating agents, clarifying agents, UV absorbers, light stabilizers, excipients, lubricants, acid scavengers, antistatic agents, pigments and / or dyes. May further be included.

Polyol compositions according to the invention can include any suitable polyol and polyol additive. Suitable polyols include, but are not limited to, polyester polyols, polyether polyols and mixtures of the two.

Polyurethane compositions according to the invention can include any suitable polyurethane and polyurethane additives. Polyurethane products are produced via catalytic polymerization of reaction products of polyols and isocyanates. Typical polyols include both polyester polyols and polyether polyols and mixtures of the two. TDI (toluene diisocyanate) and MDI (methylene diphenyl diisocyanate) are two aromatic isocyanates, whereas HDI (hexamethylene diisocyanate) is the most commonly used aliphatic isocyanate in the polyurethane industry. When making polyurethane foams, auxiliary foaming agents such as methylene chloride, acetone, carbon dioxide may be used due to their foaming ability. Other additives such as UV absorbers and antioxidants for protecting polyurethane products from decomposition by light and / or oxygen are also used.

The seed coating composition according to the present invention can contain any suitable seed coating raw material. Suitable seed coating materials are binders, active materials (plant-enhancing additives and / or plant-protecting additives) insecticides, fungicides, defoamers, fluidizers, colorants, pearl brighteners, wetting agents, dispersions. Includes, but is not limited to, agents, thickeners, defoamers, surfactants and solvents. Suitable examples of such seed coating materials are disclosed, for example, in US Patent Application Publication No. US2017 / 0127670A1 (Bueno et al.), The disclosure of which is incorporated herein by reference.
Inducers As used herein, inducers are reactants suitable for converting a colorless or substantially colorless state to a colored state. Suitable inducers for use are any oxidizing agents known in the art other than their native (triplet) atmospheric concentration of molecular oxygen. Commercial goods, such as laundry care compositions, are manufactured, distributed across the supply chain (including transportation by car, truck, railroad, ship and plane, with or without temperature control), shelf life storage, or by external instructions. During normal use as instructed, such molecular oxygen concentrations will be encountered. The term "sufficient inducer" also does not refer to the concentration of oxidant found in sources (eg, waterworks) that will come into contact with or be mixed with the composition during normal use.

The inducer may be a halogen bleaching compound that is solid at 25 ° C. Suitable hypochlorite-producing compounds are water-soluble dry solid materials that produce hypochlorite ions upon contact with water or dissolution in it. Non-limiting examples thereof are dry particulate heterocyclic N-chlorimides such as trichloroisocyanuric acid, dichlorocyanuric acid and salts thereof, such as sodium dichlorocyanate and potassium dichlorocyanurate. Other N-chloroimides such as N-chlorosuccinimide, N-chloromaronimide, N-chlorophthalimide and N-chloronaphthalimide may be used. Additional suitable N-chloroimides are hydantoins such as: 1,3-dichloro-5,5-dimethylhydantoin; N-monochromo-C, C-dimethyl hydantoin; methylene-bis (N-chloro-C, C-dimethyl). Hydantoin); 1,3-dichloro-5-methyl-5-isobutyl hydantoin; 1,3-dichloro-5-methyl-5-ethyl hydantoin; 1,3-dichloro-5,5-diisobutyl hydantoin; 1,3- Dichloro-5-methyl-5-n-amyl hydantoin; etc. Other useful hypochlorite liberators are trichloromelamine and dry particulate water-soluble anhydrous inorganic salts such as calcium hypochlorite, calcium hypochlorite tetrahydrate and lithium hypochlorite. be.

Inducers are dichloroisosianulic acid, alkali metal dichloroisosianurate, which can be used in the form of an anhydride or one and / or dihydrate thereof, 1,3,5-trichloroisosianulic acid, alkali metal 1,3. , 5-Trichloroisocyanurate, N-chlorosulfonamide, eg alkali metal N-chloro (4-methylbenzene) sulfonamide (Chloramine® T), N-chlorosulfamate, N-halosuccinateimide, eg. N- chlorosuccinimide and / or N- bromosuccinimide, oxy calcium chloride may also be used as a mixed salt of calcium chloride and calcium hydroxide, for example _{3CaCl (OCl) · Ca (OH} ) 2 · 5H 2 It may be selected from the group consisting of O and a mixture thereof. A preferred solid halogen bleaching compound suitable for use as an inducer is alkali metal dichloroisocyanurate. Sodium is the preferred alkali metal, but lithium and potassium salts may be used.

Hydride donors may be used as inducers. Suitable hydride donors are chloranil (tetrachloro-1,4-benzoquinone), tetrachloro-1,2-benzoquinone, DDQ (2,3-dichloro-5,6-dicyano-p-benzoquinone) and mixtures thereof. It may be selected from the group consisting of.

Highly preferred inducers for use in the present invention are sodium hypochlorite, calcium hypochlorite, sodium dichlororosenurate, alkali metal N-chloro (4-methylbenzene) sulfonamide (Chloramine®). T), N-chlorosulfamate, N-bromosuccinimide, tetrachloro-1,2-benzoquinone, DDQ (2,3-dichloro-5,6-dicyano-p-benzoquinone) and mixtures thereof.

The inducer may be liquid or solid. The inducer may be pre-packaged in a single-volume aliquot. The inducer may be in the form of tablets.
Product Form Liquid When in liquid form, the laundry care composition is aqueous (typically> 2% by weight or even more than 5 or 10% by weight of total water, up to 90 or up to 80% by weight or 70% by weight. Total water) or non-aqueous (typically less than 2% by weight total water content). The composition may be in the form of an aqueous solution or a homogeneous dispersion or suspension of a surfactant, a leuco composition and certain optional other ingredients. Some of the raw materials may be in solid form, usually in combination with normally liquid components of the composition, such as liquid alcohol ethoxylate nonionic and aqueous liquid carriers. Such solutions, dispersions or suspensions may be acceptablely phase stable. If in liquid form, laundry care compositions, in 20s-1 and 21 ° C., 1 to 1500 centipoises (1~1500mPa ^* s), preferably 100 to 1000 centipoises (100~1000mPa ^* s), and most preferably It may have a viscosity of 200 to 500 centipores (200 to 500 mPa ^{* s).} Viscosity can be determined by conventional methods. Viscosity is measured using an AR550 rheometer from TA instruments using a flat steel spindle with a diameter of 40 mm and a gap size of 500 μm. High shear viscosities at 20s-1 and low shear viscosities at 0.05-1 can be obtained from the 0.1-1 to 25-1 log shear rate curves for 3 minutes at 21 ° C. The preferred rheology described therein may be achieved by using the internal structuring with a detergent feedstock or by using an external rheology modifier. The liquid detergent composition may have a high shear rate viscosity of about 100 centipores to 1500 cmpores, more preferably 100 to 1000 cps. The washing flexible composition may have a high shear rate viscosity of 10 to 1000, more preferably 10 to 800 cps, most preferably 10 to 500 cps.

Laundry care compositions are prepared by combining the ingredients in any convenient order and by mixing the resulting ingredient combinations, eg, stirring, to form a phase stable liquid laundry care composition. Can be done. In the process for preparing such compositions, at least most or even substantially all of the liquid components, such as non-surfactants, non-surfactant liquid carriers and other optional liquid components. A liquid matrix containing the above is formed, and the liquid components are thoroughly mixed by imparting shear agitation to this liquid combination. For example, rapid stirring with a mechanical stir bar may be usefully used. Virtually all of any anionic surfactant and solid form feedstock can be added while shear agitation is maintained. Stirring of the mixture may be continued, and if necessary, increased at this point to form a solution of insoluble solid phase fine particles or a homogeneous dispersion in the liquid phase. After some or all of the solid form material has been added to this stirred mixture, particles of any enzyme material contained, such as enzyme prills, may be incorporated. As a modification of the composition preparation procedure described above, one or more solid components are added to the stirred mixture as a solution or slurry of particles premixed with a small portion of one or more liquid components. May be good. After all the addition of the composition components, stirring of the mixture may be continued for a period sufficient to form a composition with the required viscosity and phase stability characteristics. Frequently, this involves agitation over a period of about 30-60 minutes.

The liquid laundry detergent composition may contain less than about 50%, even less than about 40%, or even less than about 30% water by weight. The liquid laundry detergent composition may contain from about 1% to about 30%, or even from about 2% to about 20%, or even from about 3% to about 15% water by weight. Water and other ingredients in the laundry care composition may be free of any inducers.
The pouch laundry care composition is in the form of a single package, a tablet or preferably a liquid / solid (optionally granule) / gel / paste held in a water-soluble membrane known as a pouch or pod. It may be provided by either. The laundry care composition may be encapsulated in a single or multi-compartment pouch or pod. The multi-compartment pouch is described in more detail in EP-A-2133410. If the laundry care composition is present in a multi-compartment pouch, it may be in one or more compartments, therefore the leuco composition is in one or more compartments, optionally all compartments. It may be present in. Non-shading dyes or pigments or other aesthetics may be used in one or more compartments. The composition may be present in a single compartment of the multi-compartment pouch. The leuco composition may be incorporated into the membrane material of the pouch.

Preferred membrane materials are polymeric materials. Membrane materials can be obtained, for example, by casting, blow molding, extrusion or blow extrusion of polymeric materials, as is known in the art. Suitable polymers, copolymers or derivatives thereof for use as pouch materials are polyvinyl alcohol, polyvinylpyrrolidone, polyalkylene oxides, acrylamide, acrylic acid, cellulose, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetate, It is selected from polycarboxylic acids and salts, polyamino acids or peptides, polyamides, polyacrylamides, maleic / acrylic acid copolymers, polysaccharides containing starch and gelatin, natural gums such as xantane) and cara gum. More preferred polymers are selected from polyacrylate and water soluble acrylate copolymers, methyl cellulose, sodium carboxymethyl cellulose, dextrin, ethyl cellulose, hydroxyethyl cellulose, hydroxypropylmethyl cellulose, maltodextrin, polymethacrylate, most preferably polyvinyl alcohol, polyvinyl alcohol copolymers and It is selected from hydroxypropylmethylcellulose (HPMC), as well as combinations thereof. Preferably, the level of the polymer in the pouch material, eg PVA polymer, is at least 60% by weight. The polymer can have any, preferably about 1000-1,000,000, more preferably about 10,000-300,000, even more preferably about 20,000-150,000 weight average molecular weight. .. A mixture of polymers can also be used as the pouch material. This can be useful for controlling the mechanical and / or dissolving properties of the compartment or pouch, depending on its application and required needs. Suitable mixtures include, for example, mixtures in which one polymer has higher water solubility than another polymer and / or one polymer has higher mechanical strength than another polymer. Also, a mixture of polymers having different weight average molecular weights, such as PVA or copolymers thereof having a weight average molecular weight of about 10,000 to 40,000, preferably around 20,000, and about 100,000 to 300,000. A mixture of PVA or a copolymer thereof having a weight average molecular weight of about 150,000 is also preferable. Also preferred here are those obtained, for example, by mixing polylactide and polyvinyl alcohol, including hydrolyzable and water-soluble polymer blends such as polylactide and polyvinyl alcohol, typically about. A polymer blend composition comprising 1-35% by weight of polylactide and approximately 65% to 99% by weight of polyvinyl alcohol. Preferred for use here are polymers that are hydrolyzed from about 60% to about 98%, preferably from about 80% to about 90% to improve the dissolution characteristics of the material.

Different membrane materials and / or different thicknesses of membranes may be used in making the compartments. The benefit of choosing different membranes is that the resulting compartments can exhibit different solubility or release characteristics.

The most preferred membrane materials are PVA membranes known in MonoSol Authorization Qualification M8630, M8900, H8779, those described in US Pat. Nos. 6,166,117 and US Pat. No. 6,787,512, as well as the corresponding solubility. And a PVA membrane with deformed features.
Washing Care Ingredients Washing care compositions include surfactants, anionic surfactants, nonionic surfactants, cationic surfactants, polyethylene glycol polymers, ethoxylated polyethyleneimines, rheology modifiers, hue-imparting dyes, dyes. Transition Inhibitors, Aesthetic Colorants, Encapsulated, Fragrances, Perfume Microcapsules, Fragrance Delivery Systems, Odor Reduction Materials, Textile Softeners, Chelating Agents, Enzymes, Enzyme Stabilizers, Catalytic Materials, Tannins, Stain Release Polymers, Silicones , Polymer wax, latex, oily sugar derivative, cationic polysaccharide, polyurethane, fatty acid, enzyme stabilizing system, antioxidant, opalescent agent, pearl brightener, deposition aid, builder, dispersant, bleaching agent, bleaching activator , Blowing catalysts, organic shine polymers, surfactants, foam inhibitors, metal care agents, metal salts, corrosion inhibitors, and mixtures thereof.

The laundry care composition may contain from about 1% to about 80% of the surfactant by weight of the detergent or cleaning composition. The surfactant may be selected from the group consisting of anionic, nonionic, amphoteric, zwitterionic, amphoteric, semipolar, cationic surfactants, or mixtures thereof. The surfactant may be selected from the group consisting of anionic, nonionic, cationic surfactants and mixtures thereof. Surfactant systems typically contain anionic and nonionic surfactants by weight. The weight ratio of the anionic surfactant to the nonionic surfactant is about 1.1: 1-4: 1, preferably about 1.2: 1 to about 3: 1, or preferably about 1. It may be 5: 1 to about 2.5: 1, or even more preferably about 2: 1.

The laundry care composition may contain enzymes. Enzymes include hemicellulase, peroxidase, protease, cellulase, xylanase, lipase, phosphorlipase, esterase, cutinase, pectinase, keratanase, reductase, oxidase, phenoloxidase, lipoxygenase, ligninase, pullulanase, tannase, pentosanase, malanase, β-glucanase, arabicase. It may be selected from the group consisting of nosidases, hyaluronidases, chondroitinase, laccases and amylases, or mixtures thereof.

The detergent or cleaning composition may contain a polymer. The polymer may be a carboxylate polymer, a polyethylene glycol polymer, a terephthalate polymer, an amine polymer, a cellulose-based polymer, a dye transfer inhibitory polymer, a dye lock polymer, for example, a condensed oligomer produced by condensation of imidazole and epichlorohydrin, optionally 1: It may be selected from a hexamethylenediamine derivative polymer, ethoxylated polyethyleneimine and any combination thereof in a 4: 1 ratio.

The laundry care composition may contain other suitable ingredients that, on some aspects, can be incorporated wholly or partially. The ingredients may be selected according to the intended function of the laundry care composition. In some aspects, in the case of a multi-compartment single-volume packaged article, the laundry care ingredient is not the first encapsulated in a compartment separate from the first laundry care composition (eg, second, Third, fourth, etc.) It may be a part of the composition. The non-first composition may be any suitable composition. The non-first composition may be in the form of a solid, liquid, dispersion, gel, paste or mixture thereof. If the single package contains multiple compartments, the leuco composition may be added to, or may be present in, one, two, or even all compartments. Concentrating the antioxidant with the leuco composition in a smaller volume compartment may lead to higher local concentrations of the antioxidant, which may provide enhanced stability. Thus, as one of skill in the art will understand, the formulator can choose the location and amount of leuco composition according to the desired properties of the single-volume packaging.
Methods of Use The present disclosure also relates to methods of detecting an authentic composition. The methods are: a) preparing a composition having a first color containing at least one leuco composition; b) adding an inducer to the composition; c) first color in the composition. It may include a step of detecting a change from to a second color. The presence of the Leuco composition of the claimed invention in the authentic composition can identify the authentic composition from the counterfeit composition. The presence of the Leuco composition of the claimed invention does not affect the quality or functionality of the composition through production, transportation, storage or use.

The leuco composition changes from a colorless or substantially colorless state to a colored state upon exposure to sufficient inducers. This change in the leuco composition is sufficient to affect the color of the composition and change it from the first color to the second color. The color change of the composition can be detected by the user either visually or spectrophotometrically, demonstrating that the composition is authentic. The color change of the composition can be determined according to the method presented in the section of test methods below. Lack of color change may indicate that the composition is not authentic.

Lower levels of leuco compositions may be used in compositions having a first color that is only substantially colorless or lightly colored. If the composition has a first color that is more intensely colored, higher levels of leuco composition may be required to achieve a recognizable change in appearance after addition of the inducer. If the first color state is a particularly dark color, the composition is diluted with a suitable solvent or medium (eg, deionized water) prior to adding the inducer, thereby diluting the first color. It may be advantageous to make the change in appearance from state to second color state more easily perceived. Appearance changes are easier to recognize when comparing two samples side-by-side, and instructions for detecting color changes are performed with a first color and a second color contrast comparison. It may include ensuring that. In other cases, no control comparison is required and the visual examination when adding the inducer reveals a significant change in appearance to the person performing the detection and the product is authentic. It will be enough to convince you that you have established that.

The methods are a) a step of preparing a composition having a first color containing at least one leuco composition; b) a step of adding an inducer to the composition, wherein the inducer is as described above. A step sufficient to achieve a change from a colorless state to a colored state in a leuco composition conforming to formula (I); c) a step of detecting a change from a first color to a second color. And may be included. In the method, the composition and the inducer may be combined in any suitable manner. For example, the composition and colorant may be combined in a suitable vessel and the color of the combined composition and inducer is monitored to observe any color change. Alternatively, the composition may be applied to a surface or substrate (eg, card or test strip) on which the inducer is deployed. In such an embodiment, the color of the composition applied to the surface can be compared to the color of the initial composition to determine if any change in color has occurred.
Certification Test Kits Test kits may be used to detect whether a composition is genuine or counterfeit. Kits can be found in various facilities, such as customs warehouses, retail stores, wholesale suppliers, manufacturing plants, distributors, pay-as-you-go facilities, consumer homes, or anywhere else where suspected counterfeit products can be found. In one or more, it may be configured for field use. The kit enables rapid and effective on-site detection of counterfeit products without the need for expensive analytical equipment, highly trained test technicians or complex experimental procedures.

The test kit for detecting the authentic composition is preferably (a) a container for receiving a certain amount of the composition; (b) a leuco composition conforming to the formula (I) as described above [in the formula]. , Ar ² and Ar ³ are independently carbocyclic aryls or heteroaryls, and Ar ¹ is selected from the group consisting of unsubstituted phenyl, electron-deficient carbocyclic aryls and heteroaryls]. Includes the inducer; (c) the composition and instructions for combining the inducer to detect the authentic composition. The test kit may include two containers for receiving a certain amount of composition. The second container may be used to receive a certain amount of composition that can be used as a negative control to allow control comparisons that make visual determination of color change easier.

The instructions for the test kit may be in the form of written instructions, pictorial instructions, audio instructions, visual instructions, or a set of various combinations of these instruction types. Instructions for the kit may include a color index. The Color Index may illustrate various colors that indicate the authentic composition after combination with the inducer of the composition. The various colors that indicate an authentic composition will depend on the composition and the first color of the particular leuco composition selected. In a non-limiting example, a color index having a series of green hues is substantially colorless and comprises a furfural leuco composition, eg, a leuco composition conforming to Formula IV above, which exhibits green color upon induction. It may be included in the instructions for a kit configured to detect the authenticity of a composition having one color.

The instructions may include sample preparation instructions. The sample preparation instructions may instruct the user to dilute the composition sample prior to the addition of the inducer.
Combination A. Equation (I):
Ar ¹ Ar ² Ar ³ CH (I)
[In the formula, Ar ² and Ar ³ are independently carbocyclic aryls or heteroaryls, and Ar ¹ is selected from the group consisting of unsubstituted phenyl, electron deficient carbocyclic aryls and heteroaryls. ] Containing a leuco composition comprising at least one leuco composition conforming to.

B. Item A. The composition of Item A, wherein Ar ¹ is selected from the group consisting of unsubstituted phenyl, nitro-substituted carbocyclic aryl, furan, thiophene, pyridine and indole, preferably furan.

C. At least one of Ar ² and Ar ^3, preferably both Ar ² and Ar ³ is a phenyl ring substituted with an electron donating group, Section A or composition according to any one of B.

D. Item C. The composition of Item C, wherein the electron donating group is a substituted amine covalently bonded to the phenyl ring at the para position with respect to the carbon atom connecting the three Ar groups.

E. The substituted amine is the formula-NR ⁴ R ⁵ [in the formula, R ⁴ and R ⁵ are H, C _1-16 branched alkyl, C _1-16 linear alkyl, C _1-16 substituted alkyl, respectively. , C _1-16 substituted linear alkyl, C _7-16 substituted alkaline, C _7-16 unsubstituted alkaline, polyoxyalkylene, and mixtures thereof independently selected from the group]. Item D composition.

F. Item E. The composition of item E, wherein at least one R ⁴ or R ⁵ is a polyoxyalkylene containing 3-60 ethylene oxide repeating units.

G. Item E. The composition of item E, wherein R ⁴ and R ⁵ are polyoxyalkylenes comprising 3 to 60, preferably 10 to 25 ethylene oxide repeating units.

H. A method of detecting an authentic composition,
a. A step of preparing a composition having a first color, wherein the composition is of formula (I) :.
Ar ¹ Ar ² Ar ³ CH (I)
[In the formula, Ar ² and Ar ³ are independently carbocyclic aryls or heteroaryls, and Ar ¹ is selected from the group consisting of unsubstituted phenyl, electron deficient carbocyclic aryls and heteroaryls. ] Containing a leuco composition comprising at least one leuco compound conforming to the step;
b. A step of adding an inducer to a composition, wherein the inducer changes at least one leuco composition from a colorless state to a colored state;
c. A method comprising a step of detecting a change, wherein the change from the first color to the second color is visually perceptible.

I. Item I method, wherein the change from the first color to the second color has a color change score (DE ^{*) of at least 2.}

J. The method of any of Items I and J, wherein Ar ¹ is selected from the group consisting of unsubstituted phenyl, nitro-substituted carbocyclic aryl, furan, thiophene, pyridine and indole, preferably furan.

K. Ar ² and Ar ³ are independently selected according to ^{formula -NR 4} R ⁵ where Ar 2 and Ar 3 are covalently bonded to their respective phenyl rings at the para position with respect to the carbon atom connecting the three Ar groups. Phenyl rings with substituted amines, respectively, where R ³ and R ⁴ , respectively, are H, C _1-16 branched alkyl, C _1-16 linear alkyl, C _1-16 substituted branched alkyl, C _{1 to 16} substituted linear _{alkyl, C 7 to 16} substituted _{alkaryl, C 7 to 16} unsubstituted alkaryl, polyoxyalkylene, and are independently selected from mixtures thereof, claim I, one of J and K Method.

L. Inducing agents are sodium hypochlorite, calcium hypochlorite, sodium dichlororosenurate, alkali metal N-chloro (4-methylbenzene) sulfonamide, N-chlorosulfamate, N-bromosuccinimide, tetrachloro. The method of any of Items I, J, K and L selected from the group consisting of -1,2-benzoquinone, DDQ (2,3-dichloro-5,6-dicyano-p-benzoquinone) and mixtures thereof. ..

M. A test kit for detecting authentic compositions,
a) With a container to receive a certain amount of composition;
b) Formula (I) in the composition:
Ar ¹ Ar ² Ar ³ CH (I)
[In the formula, Ar ² and Ar ³ are independently carbocyclic aryls or heteroaryls, and Ar ¹ consists of unsubstituted phenyl, electron-deficient carbocyclic aryls and heteroaryls. Selected from the group] with an inducer that converts from colorless to colored.
c) A test kit that includes instructions for detecting the authentic composition by combining the composition and the inducer.

N. Item N test kit with instructions including color index.
Test method I. Determination of Electron-Deficient Carocyclic Aryl If the carbocyclic aryl group has multiple substituents, or if the structure of the leuco composition is unknown, then the carbocyclic aryl group is electron-deficient using the following method. It is possible to determine whether or not it is. For the purposes of the present invention, the carbocyclic aryl group has a color formation rate during storage for the following two species.

If the order is, it is considered that there is an electron deficiency, and in the formula, the subscript a is 1 to 5, and R is not H in the sample. If the proportion of the sample composition carrying the independently selected R substituent is greater than or equal to the proportion of the control composition exemplified on the right, then the carbocyclic ring (Ar ¹ ) in the sample composition is , Not lack of electronics. The control composition is CAS No. 129, available from 4,4'-(phenylmethylene) bis [N, N-dimethylbenzeneamine], TCI America Research Chemicals, Portland, OR, 97203, also known as leucomal malachite green. -73-7. A sample leuco composition and a control leuco composition are prepared from 2 equivalents of N, N-dimethylaniline and the aldehydes shown below, respectively, by standard methods.

Alternatively, the control leuco composition may be purchased as described above. Incorporate 3.00 × 10 ^-4 mol kg of leuco compounds of the composition and prepare the target composition from each leuco compound. Using a cuvette with a path length of 1.0 cm, the initial absorbance spectrum of each composition and those of the sample composition containing no leuco compound are measured at 400-750 nm. Determine the initial differential absorbance spectrum. The initial differential absorbance spectrum for the sample compound can be found by subtracting the initial absorbance value for the leuco-free composition from the initial value for the composition containing the sample leuco compound. The initial differential absorbance spectrum for the control composition can be found by subtracting the initial absorbance value for the leuco-free composition from the initial value for the composition containing the control leuco compound.

The three samples are stored in a closed container at 50 ° C. in the dark for 12 weeks, then the samples are removed, cooled to room temperature and the final absorbance spectra of each of the three compositions are measured. The final differential absorbance spectra for the sample and control are determined in a manner similar to the initial differential spectrum determination described above. For each of the triphenylmethane dyes formed from each leuco composition, the change in the difference spectrum from the beginning to the end at the lambda maximum is determined. For the control leuco composition, the triphenylmethane dye formed is CAS No. 14426-28-9, available from Malachite Green, BOC Sciences, Shirley, NY, 11967. If, at the wavelength of their respective lambda maximum, no clear local maximum absorbance in units of at least 0.1 absorbance is seen in the change in the difference spectrum of at least one of the sample composition or control composition, then sample. Return to storage as before for an additional 4 weeks and repeat the measurements. Repeat as necessary until at least one local maximum absorbance in units of 0.1 absorbance is seen in the change in the difference spectrum of at least one of the sample composition or control composition at the wavelength of their respective lambda maximum.

Triphenylmethane dyes formed from the respective leuco compositions when the change in the differential absorbance spectrum of at least one of the sample composition or control composition has a distinct local maximum absorbance in units of at least 0.1 absorbance. Compare the two values of absorbance at the individual lambda maximums of. The difference in the absorbance spectrum for the composition with the sample leuco composition is for the triphenylmethane dye (malachite green) formed from the control leuco colorant composition in the differential absorbance spectrum for the composition with the control leuco colorant composition. If the triphenylmethane dye formed from the sample leuco composition has the lambda maximum absorbance, which is lower than the lambda maximum absorbance, then the R substituent independently selected in the sample leuco colorant composition. The containing aryl ring is considered to be electron deficient.
II. Detection of Color Changes in Compositions Changes in the first color to the second color in the compositions of the present disclosure have been detected using any suitable method, including visual or spectrophotometric methods. May be good.

The color change of the composition may be detected by spectrophotometric analysis as described later. ^{The L *} , a ^* and b ^* values of the composition sample before and after the addition of the inducer are collected. The color change score (DE ^* ) is calculated by the following equation:
DE ^* = ((L ^* _i- L ^* _f ) ² + (a ^* _i- a ^* _f ) ² + (b ^* _i- b ^* _f ) ² ) ^1/2
In the formula, the subscripts i and f are the composition before the addition of the inducer (first or initial (i) color) and the composition after the addition of the inducer (second or second). The final (f) color).

Depending on the first color of the composition, the color change of the composition from the first color to the second color is DE ^* = 2 especially when comparing the first color and the second color side by side. .0 and above may be visually perceptible. In some cases, the amount of leuco composition used in the composition is such that the change in color (DE ^* ) between the first and second colors is at least about 5, or even at least about. It may be preferable to adjust it to 10. This ensures that color changes are easily recognizable by visual inspection and enhances certainty in identifying genuine products from non-genuine products.

Such factors are well known to those of skill in the art and are known to those of skill in the art for selecting leuco compositions, incorporating leuco compositions into laundry care formulations at appropriate levels, selecting suitable inducers, and detecting color changes. Developing easy-to-understand and easily compliant instructions for a person skilled in the art is a routine matter for a person skilled in the art.
Spectrophotometric analysis to determine L ^* , a ^* , b ^* , saturation (C ^* ) and hue (h ^{*) of the composition:}
The aesthetic appearance of the composition is a LabScan XE reflection spectrophotometer (HunterLabs, Reston, VA; D65 illumination, 10 ° observer, UV light exclusion), sample cup, ring and disc set, sample cup port insert and Measurement is performed using a translucent sample set (part number LSXE-SC-ASSY) including an opaque cover. Step-by-step instructions can be found in Hunter Labs Applications Note, Vol. 11, No. 3, 2008.

The purpose of the ring and disc set is to control the liquid characteristics associated with the translucent liquid samples and the interaction of excess light (diffusion and transmission), and therefore these samples are rather measured by the sensor. Make an opaque sample designed to.

When a set of rings and discs is used to measure a liquid, a black plastic ring is first placed in the sample cup to determine the internal path length of the light through the liquid sample, excluding external light that can cause measurement interference. Fix to 10 mm. Pour the liquid into the cup until the level of the liquid is above the top of the black ring.

Place the white ceramic disc in the liquid until it rests on the top of the ring. The disc provides a white background to direct the light transmitted to the detector by the liquid return. A black sample cup cover is then placed on the sample cup to prevent any ambient light from outside the device from leaking into the detector. Liquid samples are measured through the bottom of a crystal sample cup of excellent optical quality as part of a set of rings and discs and used with the accompanying port insert. The following are step-by-step instructions for using a set of rings and discs.
1. 1. Orient the instrument so that the sample port faces up. Replace the regular port insert with a special port insert for the sample cup.
2. 2. Standardize equipment with special port inserts in place.
3. 3. A 10 mm black ring is inserted into the cup so that it rests flat on the bottom of the cup.
4. Fill the cup with a liquid sample until the liquid exceeds the level of the ring.
5. The white ceramic disc is suspended through the liquid sample until it has settled on the top of the black floating ring. The goal is to make the sample look smooth and opaque through the bottom of the glass in the sample cup.
6. Place the sample cup in the equipment port and cover it with an opaque cover.
7. Measure the sample and record the color values.
8. Pour the sample from the sample cup, refill it and measure again. An averaging of three reads is required, with liquid replacement between reads.
Formulation Examples The following are exemplary examples of laundry care compositions according to the present disclosure and are not intended to be limiting.

Examples 1-7
Heavy Liquid Laundry Detergent Composition

Total cleaning and / or treatment Based on composition weight. Enzyme levels are reported as raw material.

Examples 8-18
Single Volume Packaging Compositions These examples provide various formulations for single volume packaging laundry care compositions. Compositions 8-12 include a single single-volume packaging compartment. The membrane used to encapsulate the composition is a polyvinyl-alcohol based membrane.

Based on total laundry care composition weight. Enzyme levels are reported as raw material.

In the example below, the single-volume packaging has three compartments, but similar compositions can be made with any number of compartments. The membrane used to encapsulate the compartment is polyvinyl alcohol.

Based on the total laundry care composition weight, enzyme levels are reported as raw material.

AE1.8S is C _12-15 alkylethoxy (1.8) sulfate AE3S is C _{12-15 alkylethoxy (3) sulfate AE7 is a C 12-13} alcohol with an average ethoxylation degree of 7. _{The ethoxylate AE8 is a C 12-13} alcohol ethoxylate with an average ethoxylation of 8 _{AE9 is a C 12-13} alcohol ethoxylate with an average ethoxylation of 9 Amylase 1 by Novozymes the supplied Stainzyme (registered trademark), amylase 2 is 15mg active substance / g is, Natalase supplied by Novozymes (TM), the aS is 29mg active substance / _g, are _{C 12 to 14} alkyl sulfates Xyloglucanase is Whitezyme®, 20 mg active substance / g supplied by Novozymes. Chelating agent 1 is diethylenetriaminepentaacetate. Chelating agent 2 is 1-hydroxyethane 1,1-diphosphonic acid. Dispersin B is a glycoside hydrolase reported as 1000 mg active substance / g DTI is poly (4-vinylpyridine-1-oxide) (eg Chromabond S-403E®) or poly (1-vinylpyrrolidone). -Co-1-vinylimidazole) (eg, Sokalan HP56®).

Dye Control Agent A dye control agent according to the present invention, for example, Superex® O.D. IN (M1), Nylovixan® P (M2), Nylovixan® PM (M3) or Nylovixan® HF (M4)
HSAS is a medium-branched alkyl sulphate as disclosed in US 6,020,303 and US 6,060,443 LAS is a linear alkylbenzene sulfonate having an _{average aliphatic carbon chain lengths C 9 to} C _15. (HLAS is an acid form).

Leuco Composition Any suitable Leuco composition or mixture thereof according to the present disclosure.

Lipase is Lipex®, 18 mg active substance / g supplied by Novozimes Liquitint® V200 is a thiophene azo dye provided by Milliken Mannanase is Mannaway (registered) supplied by Novozimes. Trademark), 25 mg active substance / g nuclease is phosphodiesterase SEQ ID NO: 1 reported as 1000 mg active substance / g Optical brightener 1 is disodium 4,4'-bis {[4-anilino- The optical brightener 2, which is 6-morpholino-s-triazine-2-yl] -amino} -2,2'-stilbene disulfonate, is a disodium 4,4'-bis- (2-sulfostylyl) biphenyl. Optical brightener 3 (sodium salt) is Optiblanc SPL10® from 3V Sigma The perfume encapsulation is a core-shell melamine formaldehyde perfume microcapsule.

Abrasive enzyme is a para-nitrobenzyl esterase reported as 1000 mg active substance / g Polymer 1 is bis ((C ₂ H ₅ O) (C ₂ H ₄ O) n) (CH ₃ ) -N ⁺ - C _x H _2x −N ⁺ − (CH ₃ ) − bis ((C ₂ H ₅ O) (C ₂ H ₄ O) n) [where n = 20 to 30, x = 3 to 8] or Its sulfated or sulfonated variant Polymer 2 is ethoxylated (EO ₁₅ ) tetraethylenepentamine Polymer 3 is ethoxylated polyethyleneimine Polymer 4 is ethoxylated hexamethylenediamine Polymer 5 is Polymer 305, Acusol 305 provided by Rohm & Haas, is a polyethylene glycol polymer grafted with a vinyl acetate side chain provided by BASF.

The protease is Purefect Prime®, 40.6 mg active substance / g supplied by DuPont. The structuring agent is hydrogenated castor oil. Synthesis of Leuco Compositions The following examples are provided to further illustrate Leuco compositions; however, they should not be construed as a limitation. Although exemplary routes for synthesizing leuco compositions have been disclosed, synthesis should not be limited to these examples and synthetic routes alone. Additional starting materials and / or reagents for different synthetic routes and / or different leuco compositions not exemplified herein are also contemplated. In fact, it will be apparent to those skilled in the art that various modifications and variations may be made without departing from the scope and intent of the present disclosure. All parts and percentages mentioned in these examples are weights unless otherwise indicated.
Synthesis of leuco composition:
Leuco Composition Example 1～3,5～7 and Comparative Example 8, Ar ¹ group is described for ^Ar 1 -C (O) are derived from the H is readily adaptable composition, specifically the following general Prepared according to the above process.

The four-necked flask is equipped with an overhead stirrer, condenser, temperature controller, heating mantle and nitrogen inlet. Then, about 2 mol of the coupler (usually ^{giving rise to the radicals Ar 2} and Ar ³ in formula (I)) is added to the flask and heated to about 65-71 ° C. ^{During heating, about 1 mol of Ar 1-} C (O) H pre-dissolved in a small amount of water and a catalytic amount (about 0.4 mol) of urea are added. After mixing the above chemicals, about 1.2 mol of hydrochloric acid (in the form of muria acid) is added dropwise to control the temperature below 90-100 ° C. After the addition of hydrochloric acid, the reaction is stirred at 95-100 ° C. for about 7 hours.

Multiple methods can be used to recover the leuco colorant synthesized by the above process. One method is to neutralize the reaction product to a pH of about 9 and remove the water by rotary evaporation under reduced pressure. The resulting viscous material is diluted with an organic solvent, such as isopropanol, and filtered to remove the inorganic salt. The organic solvent is evaporated to obtain the final product.

Leuco Composition Example 4 was prepared as described herein. In a 50 mL round bottom flask, 1.5 g (10.05 mmol) of p-dimethylaminobenzaldehyde and 2.77 g (21.12 mmol) of 1-methylindole are dissolved in 10 mL of acetonitrile. Add a few drops of methanesulfonic acid to the solution. The flask is then closed with a stopper, the reaction is stirred with a magnetic stir bar, and the plate is cultured overnight at room temperature. The formed product precipitates during this process and is collected by filtration. ¹ Confirm the structure and purity of the material by 1 H-NMR.

II. Stability of laundry care compositions containing leuco compositions.

The examples below demonstrate the stability of a leuco composition as described in this disclosure. The leuco composition as described in the present disclosure resists the change from colorless to the colored state under conditions that change the other leuco dyes to the colored state.

Seven different liquid detergent samples, each containing one leuco composition as described in the present disclosure, using a dye-free AATCC 2003 liquid reference detergent containing no colorants or optical brighteners. Samples 1-7) were prepared. Sample 8 contained the Leuco composition LCV-4EO as a positive control. Liquid detergent samples 1-7 contained 0.04 wt% leuco composition and sample 8 contained 0.01 wt% leuco composition. Samples were prepared and stored in glass jars at 50 ° C. for 56 days. Visible absorbance spectra of each detergent were measured on days 0 (the day the detergent was prepared), days 7, 14, 28 and 56 of storage. The change in absorbance over time at _{the λ max} value for each Leuco-containing detergent sample _{(Δλ max} = (λ _max ) _t − (λ _max ) ₀ ) was tracked over the course of sample storage, where t is: It is the number of days, where (λ _max ) ₀ is the absorbance at _{λ max} for each detergent solution on that preparation date.

Leucomal malachite green is available from Aldrich Chemical Company, St. Purchased from Louis, Missouri. Six additional leuco compositions were prepared according to the general methods disclosed herein. The structure for the sample is provided in Table 1 below. _{For the λ max} value of the colored state for each leuco composition, take an aliquot of each HDL sample, prepare a 1:10 diluted solution with deionized water, and prepare 2,3-dichloro-5,6-dicyano-p. -Determined by oxidizing to the corresponding triarylmethane dye with an ethanol solution of benzoquinone and measuring the visible absorbance spectrum of each diluent at 400-700 nm using a UV-Vis spectrophotometer.

_{The change in absorbance over time at the λ max} value for Leuco Compositions 1-7 can be seen in Table 2 as compared to the change in absorbance in the positive control sample 8. Samples 1 to 7 showed very small changes in absorbance over time compared to sample 8.

III. Certification Tests for Laundry Care Compositions Changes from the first color to the second color in the laundry care compositions of the present disclosure are detected using both visual and spectrophotometric methods. In this example, the certification test comprises the following general procedure for each formulation tested.
(1) A 1: 5 diluted solution is prepared by mixing 20.0 mL of the laundry care composition with 80.0 mL of deionized water.
(2) The spectrophotometric method disclosed herein measures the first color of the diluted formulation from step (1) above.
(3) The inducer (0.200 mL solution of 0.031 MN-bromosuccinimide in ethanol) was added to 50.0 mL of the diluted formulation from step (1) above to give. Shake the solution for 1 minute.
(4) Perform a visual evaluation to determine if the difference between the first color and the second color of the diluted formulation is easily perceived.
(5) The second color of the diluted, induced formulation from step (3) above is measured by the spectrophotometric method disclosed herein.
^{(6) A color change score (DE *} ) is calculated for the change in appearance between the first color and the second color.

Certification tests were performed on laundry care formulations A1 and C1, each prepared from the AATCC Standards (HE) liquid detergent WOB (obtained from AATCC, June 2017), which contains neither colorants nor optical brighteners, respectively. Was done. Formulation A1 comprises 0.04% by weight of the Leuco composition according to the invention and represents a genuine product. Formulation C1 is free of any leuco composition and represents a counterfeit product. The results are shown in the table below.

The dimensions and values disclosed herein should not be understood as being strictly limited to the exact numbers listed. On the contrary, unless otherwise specified, each such dimension is intended to mean both the listed values and the functionally equivalent range around the values. For example, the dimension disclosed as "40 mm" is intended to mean "about 40 mm".

All documents cited herein, including any cross-reference or related patents or applications and any patent application or patent for which this application claims priority or interest, are referenced unless expressly excluded or otherwise limited. The whole thing is incorporated here. Citation of any document is that it is prior art relating to any invention disclosed or claimed herein, or it may be used alone or in any combination with any other reference. , Is not an approval to teach, suggest or disclose any such invention. In addition, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in the document incorporated by reference, the meaning or definition assigned to that term in this document shall prevail. And.

Although specific embodiments of the invention have been illustrated and described, it will be apparent to those skilled in the art that various other modifications and modifications can be made without departing from the spirit and scope of the invention. Accordingly, the appended claims are intended to cover all such modifications and modifications within the scope of the invention.

Claims (14)

A composition selected from the group consisting of a fragrance composition, a fuel composition, a lubricating oil composition, a thermoplastic polymer composition, a polyol composition, a polyurethane composition and a seed coating composition, wherein the composition (I):
Ar ¹ Ar ² Ar ³ CH (I)
[In the formula, Ar ² and Ar ³ are independently expressed in the formula −NR ⁴ R ⁵ [In the formula, R ⁴ and R ⁵ are H, C 1 to ₁₆ branched alkyl, C 1 to ₁₆ linear chain, respectively. From the group consisting of state alkyls, C _1-16 substituted branched alkyls, C _1-16 substituted linear alkyls, C _7-16 substituted alkalils, C _7-16 unsubstituted alkalis, polyoxyalkylenes, and mixtures thereof. an independently selected] phenyl ring substituted at the para-position to the group, at least one of R ⁴ and R ⁵ are polyoxyalkylene group, Ar ¹ is electron-deficient carbon Selected from the group consisting of cyclic aryls and heteroaryls]
A composition comprising at least one leuco composition suitable for. Ar ¹ is, two Toro substituted carbocyclic aryl, furan, thiophene, are selected from the group consisting of pyridine and indole The composition of claim 1. The composition according to claim 2, wherein Ar ^{1 is furan.} The composition according to claim 1 , wherein at least one R ⁴ and R ⁵ is a polyoxyalkylene containing 3 to 60 ethylene oxide repeating units. The composition according to claim 4 , wherein R ⁴ and R ⁵ are polyoxyalkylenes containing 3 to 60 ethylene oxide repeating units. The composition of claim 5 , wherein R ⁴ and R ⁵ are polyoxyalkylenes comprising 10-25 ethylene oxide repeating units. A method of detecting an authentic composition,
a) A step of preparing a composition having a first color, wherein the composition is of the formula (I) :.
Ar ¹ Ar ² Ar ³ CH (I)
[In the formula, Ar ² and Ar ³ are independently expressed in the formula −NR ⁴ R ⁵ [In the formula, R ⁴ and R ⁵ are H, C 1 to ₁₆ branched alkyl, C 1 to ₁₆ linear chain, respectively. From the group consisting of state alkyls, C _1-16 substituted branched alkyls, C _1-16 substituted linear alkyls, C _7-16 substituted alkalils, C _7-16 unsubstituted alkalis, polyoxyalkylenes, and mixtures thereof. an independently selected] phenyl ring substituted at the para-position to the group, at least one of R ⁴ and R ⁵ are polyoxyalkylene group, Ar ¹ is electron-deficient carbon Selected from the group consisting of cyclic aryls and heteroaryls] with at least one leuco composition comprising;
b) A step of adding an inducer to the composition, wherein the inducer changes the at least one leuco composition from a colorless state to a colored state;
c) A method comprising a step of detecting the change, wherein the change from the first color to the second color is visually perceptible. The method of claim 7 , wherein the change from the first color to the second color has a color change score (DE ^* ) of at least 2. Ar ¹ is, two Toro substituted carbocyclic aryl, furan, thiophene, are selected from the group consisting of pyridine and indole The method of claim 7. The method of claim 7 , wherein the Ar ¹ heteroaryl is furan. The inducers are sodium hypochlorite, calcium hypochlorite, sodium dichlororosenurate, alkali metal N-chloro (4-methylbenzene) sulfonamide, N-chlorosulfamate, N-bromosuccinimide, tetra. The method according to claim 7 , wherein the method is selected from the group consisting of chloro-1,2-benzoquinone, DDQ (2,3-dichloro-5,6-dicyano-p-benzoquinone) and mixtures thereof. A test kit for detecting authentic compositions,
a. With a container to receive a certain amount of composition;
b. Formula (I) in the composition:
Ar ¹ Ar ² Ar ³ CH (I)
Leuco compositions suitable for [in the formula, Ar ² and Ar ³ are independently of the formula −NR ⁴ R ⁵ [in the formula, R ⁴ and R ⁵ are H, C _1-16 branched alkyl, respectively. C 1 to ₁₆ linear alkyls, C 1 to ₁₆ substituted branched alkyls, C 1 to ₁₆ substituted linear alkyls, C _{7 to 16} substituted alkalines, C _{7 to} 16 unsubstituted alkalis, polyoxyalkylenes, and theirs. a phenyl ring substituted at the para-position relative independently selected] group from the group consisting of, at least one of R ⁴ and R ⁵ are polyoxyalkylene group, Ar ¹ is a] is selected from the group consisting of electron-deficient carbon cyclic aryl and heteroaryl, converts from a colorless to a colored state, and inducing agent;
c. A test kit comprising the instructions for detecting the authentic composition by combining the composition and the inducer. The test kit of claim 12 , wherein the instructions include a color index. 12. The test kit according to claim 12 , wherein the inducer is a solid.